Hair-dressing composition



Patented Feb. 27, 1 951 f HAIR-DRESSING COMPOSITION Theodore H. Rider, Hinsdale, and Solomon D. Gershon, Chicago, 111., assignors to Lever Brothers Company, Cambridge, Mass, at corporation of Maine No Drawing. Application Maylf), 1947,

' Serial No. 749,082

14 Claims. (c1.1s7 s7$ ..-This invention relates to a composition of upon shaking the bottle for a matter of a few matter comprising an oil phase and a water phase seconds a good emulsion is formed between the which are readily emulsifiablc upon slight agitatwo phases. This is maintained for sufiicient tion and will remain emulsified for a short time length of time to pour the requisite amount of to permit use in emulsion form, but following emulsion from the bottle and apply it. As a rewhich the emulsion will break quickly to form an sult, the correct proportions of the oil phase and oil: phase and an aqueous phase with a clear interwater phase may be dispensed and applied. The face between the phases. emulsion so formed, while it is an excellent emul- In certain types of compositions it is desirable sion for the purpose described, is nevertheless tohaveboth water and oil. For example, in a fairly short lived. This is highly desirable since dressingto be appliedto the hair it is desirable it permits the two phases of the applied emulto include an oil to supplement the natural hair sion to separate after application to the hair, oils; it is also desirable to include water in the and also permits separation of the two phases composition because the application of water to of the emulsion in the bottle during the times the hair facilitates combing it, as is well known. between use, with the advantages noted above.

'The formulation'of a composition containing The problem of making a composition which both oil and water, which has all of the desirable will readily emulsify with a minimum of agitaproperties from a 'utilitari'anas well as an aestion, will. maintain the emulsion for a given thetic point ofview, presents a number of diffiperiod, and then break quickly, presents a numculties. Because of their immiscibility, difficulties ber of 'difficulties. Generally if a good emulsion arise'in application to the hair of both oil and is to be formed quickly, a Very good emulsifying water in the'correct proportions unless they are agent is required and the composition has a applied in the form of an emulsion. However, tendency to remain emulsified for a considerable 333133..lfiiiei liiiiiihllitt $222??? $32.? iii tfi tit otif 52555 5? ti fiipiiiii ii ber of difficulties and are not as ideal as might be formulated so that the emulsion breaks quickly, a m u e u h a permanent emulit generally requires extensive agitation over a men is undeslrableas' a hair dressmg because the long ueri d of tim 1 form a gQQd enough 1- component In the 1111181" phase of such a persion for initial use. Either form is undesirable for manen emulsion does not reach the hair. In ad- 0, the purposes mentioned. d the e an e 0 t e 0 1' in emu s on Another problem in connection with composif rm d 0v r;10ns" periods con r u to i i tions of thistype is that even though the requireterlo at 'on Sinc t e Water an the l' -l ment for quick emulsification and ready breaking i fil i e Often have BID-95115901113 1 of the emulsion are met, there is a tendency for fectswhen inthe' ntimate contact characteristic a thi phase t f rm between the oil and the of 't h l water phase after repeated uses of the emulsion. =11? IS an 'fl cfi lit 'WGQUO thfilefole, to This may include small amounts of materials expr 0.0 1 05 12 011 cfimtaming an oil phase tractcd from the oil or-from the water or from andan aqueous phase w h'ar wd miscible both. These materials may be solid or appear te o m ofil ulsion un n' S ight a at on and 40 as solids and may have a color different than that to'maintainlthe emulsion fortime to pe p of the oil or water. As a result, the accumulaplicfition t hair, follo ml tion of this material in the intermediate phase sion applied'to the hair breaks so that both comdetracts from the appearance of the composition, p s reach t a and th r mainin and while it may not interfere with the use of it, emulsion in the container breaks to form an oil it may give the user the impression that the comphase and an aqueous phase with a clear interposition is deteriorating in some way. faces It is a further object of my invention, therea! result of the inventionrthe oil. phase and fore, to so treat the composition during its thewaterphase are maintained'separate in the formulation so that although the composition contamer,i"exce'pt fora-single interface where may be emulsified'and the emulsion broken inthe twolayers join. The interface area exnumerable times, there will be no formation of tremely small as compared with the area of conan ill-appearing intermediate phase, and the tact in an: emulsion, especially when the volume composition will maintain a clear and sharp inof the two liquidsi is considered. When the comterrace between the oil and the water phases un-" position isfusediitsis generally. in a bottle and contaminated by any extraneous material.

The above objects of the invention are accomplished by including in the oil phase a particular oil-soluble emulsifying agent and by including in the water phase a particular water-soluble emulsifying agent. These two emulsifying agents in the separate phases coact to produce the desirable emulsifying and emulsion breaking properties described heretofore.

Inasmuch as the oil preferred is a vegetable oil normally subject to the development of rancidity, as is characteristic of all vegetable oils it is preferred to include an antioxidant in the composition, even though the oxidation of the oil is minimized because of the quick emulsion breaking properties described heretofore.

In accordance with the invention, there is in cluded an oil-soluble antioxidant in the oil phase and a water-soluble antioxident in the water phase. Although these antioxidants are in different phases, and even on emulsion are not brought in contact with each other except at the surface interface of the emulsion, there is an enhanced coaction between the two antioxidants beyond that obtained with the use of either alone in their respective phases, or which might be expected considering that the opportunity for contact between the oil-soluble antioxidant and the water-soluble antioxidant is very restricted because of their different solubilities and the separate phases in which they are contained.

The following formula sets forth a preferable embodiment of the invention. After this is set forth the various modifications which may be made in the formulation as well as the several ingredients without departing from the invention.

Oil phase Parts by weight Olive oil 7.64 Oil-soluble emulsifier 0.33 Concentrate of natural mixed tocopherols (34% concentration) 0.08 Perfume 0.21

' Water phase Parts by weight Ethyl alcohol 40.50 Water 49.80 Water-soluble quaternary ammonium compound 0.34 Sodium chloride 1.07 Sodium bitartrate l 0.03

Referring to the formulation, the oil phase is prepared by adding the oil-soluble emulsifying agent to the olive oil. The 'oil containing the oil-soluble emulsifier is then thoroughly mixed and agitated with water, following which the oil is separated from the water by standing or by centrifugation. If desired, the mixture may be saturated with carbon dioxide before separation. This action may be repeated once or as many times as desired. During this refining treatment, some of the non-oil components of the oil, which are believed to be gums, phosphoproteins, or other non-fatty components separate from the oil into the water phase. The treatment is repeated until all of the components of this type are removed from theoil, so that a clear interface is obtained. The components removed in this type of refining are those, which if left in the oil, would form the undesirable contaminating third phase between the oil and water phases in the finished product. The oil refined in this manner is free from these con- (i ll taminating properties, irrespective "bf the shelf lifeand extent of use of the final composition. It is believed that the presence of the particular emulsifier in the oil is responsible f orfthe separation of these impurities in the water during the refining, since if the oil without the emulsifier is treated with water, these impurities, are not separated in the water phase. The presence of carbon dioxide also facilitates the removal of the impurities, although this is anoptional and unnecessary refinement. As far asiis-known, the refining of oil to remove gums, phosphoproteins and other non-fatty impurities, when the oil contains an oil-soluble emulsifier which is intended to and does remain as a component of the oil is a novel refining process. 7

Preferably the topcopherols and the perfume are included in the oil phase before it is refined The aqueous phase is then made up by disso1ving the quaternary ammonium compound with sodium chloride and with the sodium bitartrate in the alcohol and water mixture and added to the oil phase. The mixture is agitated and may be filtered if desired and the temporary emulsion is then filled into bottles.

The olive oil may be replaced in whole or inpart by any non-drying vegetable oil such as cot tonseed oil, peanut oil, soybean oil, castor oil, Olive oil is preferred. The amount of the etc. oilmay be varied at will depending on the amount of oily residue the user desires to leave upon the hair. It usually would be not more than half the mixture.

The emulsifier must be soluble in the vegetable oil, and is a partial fatty acid ester of a polyhydroxy compound containing a plurality of free hydroxy groups. A preference is expressed for the partial fatty acid esters of polyalkylene oxide derivatives of a polyol in which the fatty acid tion through the hydroxy groups of the glycosidc'.

The number of such ethanol groups depends upon the proportions of the reactants and is not critical. The partial fatty acid ester is formed by esterifying one or more of the hydroxy groups with fatty acid radicals. Anyhexose or poly- :hexose may be the basis of tlieglycoside. Preferably the derivative is the partial fatty acid ester of a polyethylene oxide derivative of propylene glycol glucoside in which the number of fatty ,acid radicals is less than the number of free hydroxy groups in the partial ester. .This composition is available commercially.

The oil-soluble emulsifien foriwhich a preference is expressed may be sir-mixture, and small 1 amounts of other ingredients may be formed and and of hydroxy ethylene ethers of polyglucose.

The primary component, however, is the partial fatty acid ester 'of hydroxy ethylene ether of propylene glycol glucoside.

The'fatty' acid used in forming the partial ester may be any fatty acid having 12 or more carbon atoms and may be Saturated or unsatw rated, such as lauric, myristic, palmitic, oleic, and stearic acids. These are referred to as higher fatty acids. A preference is expressed for oleic acid since this gives the emulsifier optimum solubility properties in the oil. The amount of the oil-soluble emulsifier will vary somewhat with the exact compound or composition used and the number of 'hydroxy groups. The amount will also be dependent somewhat on the rapidity with which the emulsion is desired to be formed upon shaking and the length of time desired for the emulsion to break. The amounts in general will fall'within plus or minus 25% of the optimum expressed in the formula. and the ratio to the oil should be kept in about the same range and can bfiQSG'lGClI-Gd within this range, depending upon the precise emulsion forming and breaking properties desired.

The tocopherols (vitamin E) may be naturally occurring. or formed synthetically and those most readily available are a mixture of natural tocopherols isolated by distillation from naturallyoc curring oils. The amount used depends somewhat on the extent of the antioxidant action desired and the susceptibility of the oil to rancidity development. There is no advantage in using more than enough to obtain the antioxidant action.

"The antioxidant is not an essential component of the composition. If it is not desired to protect the oil against rancidity, or if the oil in its natural form is such as to resist rancidity for the purpose, the tocopherols may be omitted without affecting the emulsion forming and breaking characteristics of the composition. However, most oils sho ld be protected a ainst oxidation and the inclusion of the toconherols together with the complementary antioxidant in the aqueous phase is a preferred embodiment of the invention.

Any oil-soluble perfume may be used and the small amount used may vary widely, depending upon odor characteristics of the perfume and the extent and nature of the odor desired. The perfume may consist of a phenolic material or com ounds which com rise ph-nols and the phenolic component of the perfume will also act as an antioxidant in coniunction with or su plementary to the tocopherol. If the tocopherol is not used the ph nol constituents of the perfume will add antioxidant characteristics to the composition and will coact with the antioxidants in the aqueous phase. The aqueous phase is composed rimarily of alcohol and water. Ethyl alcohol, which may be appropriately denatured for the purpose, is suitable; or pro yl or isopropyl alcohol may be used. The water may be ordinary tap water or distilled water. The proportions of alcohol and water may be varied relative to each other.

The alcohol causes the composition to dry quicker, it imparts a stimulating effect to the scalp, and it causes the emulsion to break faster than an all water aqueous phase. Depending on the effects wanted, the relative amount of water to alcohol can be varied at will. If the alcohol in the alcohol-water phase is increased sufiiciently, the specific gravity of this phase will become lower and the aqueous phasw may be the upper phase. Irrespective of which phase is on top, the relative specific gravity of the oil phase and aqueous phase should be adjusted relative to each other to obtain the d sired rapidity of separation. This total amount of the aqueous phase is the complement of the oil phase.

The quatenary compound may be any cationic surface active compound comprising .an aliphatic radical containing at least 12 carbon atoms, and has the general formula where R is an aliphatic radical containing a total of at least 12 carbon atoms and X is an ion of a strong acid such as C1 or HSO4. The three valences attached to the nitrogen may be satisfied by the same or different radicals, for example the compound may be the trialkyl such as trimethyl ammonium salt, or an alkyl piperidinium salt or a pyridinium salt. The permissable variations within the aliphatic radical are too numerous to mention. A preferred type is R-C o O-a1kNHG o CH2IIT X Within this type the compound is the preferred embodiment. R, may be a hydrocarbon radical having from 11 to 17 carbon atoms. When the latter type of compound is used, the composition has antiseptic properties which is characteristic of these compounds.

The quaternary ammonium compound in the aqueous phase coacts with the oil-soluble emulsifier in the oil phase to produce the emulsion and breaking properties described heretofore. The amount of the quaternary ammonium compound em loyed may be varied in relation to the amount of the oil-soluble emulsifier, the particular configuration in the quaternary ammonium compound, and the emulsion and breaking action desired. In general the amount is in the range of plus or minus 25% of the optimum amount expressed in the formula.

The sodium chloride may be omitted if desired. It may also be replaced by a mixture of sodium tartrate and bitartrate, thereby also increasing the antioxidant activity.

The sodium bitartrate may be replaced by tartaric acid, the neutral sodium tartrate, or the corresponding potassium salts. Other acids such as citric acid and salts thereof may be used. In general, any hydroxy dicarboxylic acid may be employed such as tartaric acid, citric acid, tartronic acid, malic acid, hydroxy succinic acid and their neutral or acid alkali metal salts. The acid or salt thereof is employed in an antioxidant capacity and functions with particular effectiveness when the oil phase contains the tocopherol. This component may be omitted if antioxidant action is not desired and when included the amount is not critical, since it can comprise the total salt content.

There has been indicated heretofore the preferred embodiment of the invention together with such variations as may be made therein, without departing from the essential features thereof and all such modifications and variations are intended to be included within the following claims.

We claim:

1. An oil and water composition suitable for use as a hair dressing comprising 7.6 to 50% by 7 weight of oil and 0.25 partial fatty acid ester of a polyhydroxy compound as emulsifier in an oil phase comprising a non-drying vegetable oil as the primary ingredient and the balance being substantially 0.26 to 0.43% of a cationic surface active quaternary ammonium compound in an aqueous phase comprising alcohol, said composition being readily emulsifiable upon agitation to provide a good meta-stable emulsion which readily separates upon standing to form an oil layer and an aqueous layer.

2. The composition of claim 1 containing an oil-soluble antioxidant.

3. The composition of claim 1 wherein the polyhydroxy compound is apolyalkylene oxide derivative of a polyol.

4. The composition of claim 3 containing a tocopherol as an antioxidant.

5. The composition of claim 3 wherein the oil is 7.64% of olive oil, the amount of the oil-soluble emulsifier is 0.33% and the polyol is a propylene glycol glucoside, and the quarternary ammonium compound is 0.34% of a higher fatty pyridinium salt of a mineral acid.

6. The composition of claim 5 containing a tocopherol as an antioxidant.

7. The composition of claim 5 wherein the quarternary ammonium compound is of the formula RC 0 O C2H4NHC O CHr-N where R is an aliphatic hydrocarbon radical of 11 to 17 carbon atoms.

8. The composition of claim 7 wherein the oilsoluole emulsifier is an oleic acid derivative of the polyhydroxy compound.

to 0.41% of an oil-soluble 9. The composition of claim 7 containing 0.27%:

of tocopherol as an antioxidant.

10. The composition of claim 7 wherein the oil-soluble emulsifier is a lauric acid derivative of the polyhydroxy compound.

11. The composition of claim 7 wherein the oilsoluble emulsifier is a myristic acid derivative of the polyhydroxy compound.

12. The composition of claim 7 wherein the oil-- soluble emulsifier is a palmitic acid derivative of the polyhydroxy compound.

13. The composition of claim 7 wherein the oilsoluble emulsifier is a stearic acid derivative of the polyhydroxy compound.

14. The composition of claim 13 containing 0.27% of tocopherol as an antioxidant.

THEODORE H. RIDER. SOLOMON D. GERSHON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Harry, Modern Cosmeticology Chemical Publishing Co. Inc., N. Y., 1940, pages 225, 226, 149,

Rosenberg, Chemistry and Physiology of the Vitamins, Interscience Publishers, Inc., N. Y.,

' 1942, page 440.

Sollman, A Manual of Pharmacology, 1942, 6th ed, W. B. Saunders. 00., N. Y., page 896.

Certificate of Correction Patent No. 2,543,061 February 27, 1951 THEODORE H."RIDER ET AL. 7

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 8, list of REFERENCES CITED, under the heading OTHER REFERENCES insert the following:

Ring-Manufactwing Chemist, Sept. 1941, pages ZZZ-$14. P OSfiegcj-Jume 28, 1940, Volume .91, N0. 2371;, pages 6224425. (Oopy in and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 22nd day of May, A. D. 1951.

THOMAS F. MURPHY,

Assistant O'owwm'ssz'omt of Patents.

Certificate of Correction Patent No. 2,543,061 February 27, 1951 THEODORE H. RIDER ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 8, list of REFERENCES CITED, under the heading OTHER REFERENCES insert the following:

Ring-Manufacturing Chemist, Sept. 1941, pages fill-Q14.

Science-Jwne 28, 1940, Volume .91, N 0. 2374, pages 624-695. (0012;; in P. 0. S. L.); and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 22nd day of May, A. D. 1951.

THOMAS F. MURPHY,

Assistant Oommz'ssz'mfl of Patents. 

1. AN OIL AND WATER COMPOSITION SUITABLE FOR USE AS A HAIR DRESSING COMPRISING 7.6 TO 50% BY WEIGHT OF OIL AND 0.25 TO 0.41% OF AN OIL-SOLUBLE PARTIAL FATTY ACID ESTER OF A POLYHYDROXY COMPOUND AS EMULSIFIER IN AN OIL PHASE COMPRISING A NON-DRYING VEGETABLE OIL AS THE PRIMARY INGREDIENT AND THE BALANCE BEING SUBSTANTIALLY 0.26 TO 0.43% OF A CATIONIC SURFACE ACTIVE QUATERNARY AMMONIUM COMPOUND IN AN AQUEOUS PHASE COMPRISING ALCOHOL, SAID COMPOSITION BEING READILY EMULSIFIABLE UPON AGITATION TO PROVIDE A GOOD META-STABLE EMULSION WHICH READILY SEPARATES UPON STANDING TO FORM AN OIL LAYER AND AN AQUEOUS LAYER. 